Methods for using improved urea hydrochloride compositions

ABSTRACT

A composition including HCl, urea, complex substituted keto-amine-hydrochloride, an alcohol, an ethoxylate, and a ketone is provided in a method for solubilizing calcium carbonate in an aqueous suspension or dispersion of calcium carbonate.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part patent application of U.S.patent application Ser. No. 14/048,559, filed Oct. 8, 2013, now U.S.Pat. No. 8,430,971, which itself is a divisional application of U.S.patent application Ser. No. 13/856,469, filed Apr. 4, 2013, now U.S.Pat. No. 8,580,047, issued Nov. 12, 2013, which itself is a divisionalapplication of U.S. patent application Ser. No. 13/453,871, filed Apr.23, 2012, now U.S. Pat. No. 8,430,971, issued Apr. 30, 2013, whichitself is a divisional application of U.S. patent application Ser. No.13/104,180, filed May 10, 2011, now U.S. Pat. No. 8,163,102, issued Apr.24, 2013, which itself is a continuation-in-part patent application ofU.S. patent application Ser. No. 12/419,379, filed Apr. 7, 2009, nowU.S. Pat. No. 7,938,912, issued May 20, 2011, the disclosures of whichare herein incorporated by reference in their entirety, and all commonlyowned.

FIELD OF THE INVENTION

The present invention relates to compositions and methods for treatingfluids, and, more particularly to such compositions and methods fortreating drilling fluids in industrial applications, hydraulicfracturing, solubilizing elements, and lowering salts.

BACKGROUND OF THE INVENTION

The removal of water-insoluble cementitious and lime materials fromsurfaces is known to be a difficult process. Compositions that have beenknown for use in the past have included acid (e.g., hydrochloric,hydrofluoric, phosphoric, and sulfuric) washes and urea hydrochloridesolutions.

However, the solutions known in the art can cause corrosion and flashrusting to metal and metal alloy surfaces, and also can dissolve awaysurface coatings and underlying metals. Thus, the use of suchcompositions can decrease the life of a surface and its coatingsignificantly. For example, when used on vehicles and other industrialand construction equipment, such compositions can greatly increase thefrequency at which the treated surfaces must be re-painted, re-coated,or re-sealed.

Additionally, many prior known compositions are not environmentallysafe, and contain components that are non-OSHA and -EPA compliant. Somejurisdictions have regulations as to materials that can be drained so asto ultimately reach ground water. Resource Conservation and Recovery Act(RCRA) metals are among those substances that are regulated, and includearsenic, barium, cadmium, chromium, lead, mercury, selenium, and silver.As an example, chromium is often used as a lustrous coating on bumpers,mirrors, hydraulic rams, and trim parts on vehicles such as concretetrucks. Since construction equipment is typically washed outdoors, theresulting process water usually drains directly into the ground, and,thus, if the equipment is coated with an RCRA or other undesirablematerial that can be released with the washing composition, the materialwill enter the groundwater.

Therefore, it would be beneficial to provide a composition and method ofuse that are effective at removing cementitious materials from surfaceswithout causing corrosion or rusting, which can damage the targetsurface and release harmful substances such as RCRA materials into theenvironment. Preferably the composition should also include componentsthat are environmentally safe and OSHA- and EPA-compliant.

It would also be beneficial to provide an environmentally safecomposition and method of use that are effective in assisting inperforming hydraulic fracturing of an oil gas well, adjusting andmaintaining the pH of process water and other fluids in industrialapplications, and solubilizing calcium carbonate in an aqueoussuspension or dispersion thereof.

SUMMARY OF THE INVENTION

The application provides a method for pickling treatments, electronicsubmersible pump treatments (ESPs), hydraulic fracturing, perforationcleaning and debris removal, toe preparation treatments that replace theuse of acetic acid blends, cement squeeze treatments, injection welltreatments, disposal well treatments, pH adjustment of recycled fracwater and/or flow-back fluids, pH adjustment fluid to assist with thehydration of gelled based systems, breaking gelled fracturing systems toreplace the use of dangerous oxidizing agents, using a fluid to unsticka drilling rig, acid fracture, spearhead acid squeeze soaking, andfilter cake removal comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

A composition including HCl, urea, complex substitutedketo-amine-hydrochloride, an alcohol, an ethoxylate, and a ketone isprovided for performing hydraulic fracturing or oil or gas wells,solubilizing calcium carbonate, or lowering salt and bicarbonate levelsin irrigation systems.

A method of using the composition includes applying the composition to asurface to release a cementitious material therefrom and removing thecomposition and released cementitious material from the surface.

The composition comprises an organic, cationic inhibitor for bothcorrosion and flash rusting that minimizes pitting and attack on metaland alloy surfaces, such as are common in construction equipment andtrucks. As the composition is non-corrosive to metals, it has beendeemed non-regulated by the U.S. Department of Transportation (DOT), andis environmentally safe and OSHA- and EPA-compliant. The composition hasbeen shown to reduce corrosion levels to well below the DOT corrosionlimits of 6.25 mmpy.

In an exemplary embodiment, the inhibitor, which is used at a level ofapproximately 0.5% in the composition, comprises 10-30% surfactant,10-30% complex substituted keto-amine-hydrochloride, 1-10% 3-methylbutynol, 1-10% isopropyl alcohol, 1-10% methyl vinyl ketone, and <1%acetone. This inhibitor has been shown to substantially eliminatecorrosion of target surfaces.

A method is also provided for performing hydraulic fracturing of oil orgas wells. The method comprises providing a composition comprising HCl,urea, complex substituted keto-amine-hydrochloride, an alcohol, anethoxylate, and a ketone; and inserting the composition into an oil wellor a gas well to assist in performing hydraulic fracturing thereof.

A method is further provided for adjusting a pH of a drilling fluid. Themethod comprises providing a composition comprising HCl, urea, complexsubstituted keto-amine-hydrochloride, an alcohol, an ethoxylate, and aketone; and adding the composition to a drilling fluid for a well toassist in adjusting a pH thereof.

A method for adjusting and maintaining a pH of a process fluid comprisesproviding a composition comprising HCl, urea, complex substitutedketo-amine-hydrochloride, an alcohol, an ethoxylate, and a ketone; andadding the composition to a process fluid to adjust and maintain a pHthereof.

A method for solubilizing calcium carbonate in an aqueous suspension ordispersion of calcium carbonate comprises providing a compositioncomprising HCl, urea, complex substituted keto-amine-hydrochloride, analcohol, an ethoxylate, and a ketone; adding the composition to anaqueous suspension or dispersion of calcium carbonate; and permittingthe composition to solubilize the aqueous suspension or dispersion ofcalcium carbonate.

A method for removing a foulant from a fluid-handling element comprisesproviding a composition comprising HCl, urea, complex substitutedketo-amine-hydrochloride, an alcohol, an ethoxylate, and a ketone;adding the composition to a fouled fluid-handling element; andpermitting the composition to solubilize the foulant.

A method for removing a foulant from a surface of a marine vesselcomprises providing a composition comprising HCl, urea, complexsubstituted keto-amine-hydrochloride, an alcohol, an ethoxylate, and aketone; applying the composition to a fouled surface of a marine vessel;and permitting the composition to solubilize the foulant.

A method for lowering a salt and bicarbonate level in an irrigationsystem comprises providing a composition comprising HCl, urea, complexsubstituted keto-amine-hydrochloride, an alcohol, an ethoxylate, and aketone; diluting the composition to 5-60% by volume composition inwater; adding the composition to a fouled fluid-transporting element ofan irrigation system; and permitting the composition to solubilize thefoulant.

A method for acidizing turf and for lowering a salt and bicarbonatelevel in at least one of turf and turf growing medium comprisesproviding a composition comprising HCl, urea, complex substitutedketo-amine-hydrochloride, an alcohol, an ethoxylate, and a ketone; andadding the composition to at least one of turf and turf growing medium.

DETAILED DESCRIPTION OF EMBODIMENTS

In one embodiment according to the teachings of the present invention, acomposition comprises HCl, urea, complex substitutedketo-amine-hydrochloride, at least one alcohol, an ethoxylate, and aketone. Preferably, the HCl and the urea are present in a range of: HCl,40-60 wt %, and urea, 30-45 wt %, and, most preferably, at approximatelyHCl, 55 wt %, and urea, 42 wt %.

Preferably the alcohol comprises at least one of isopropyl alcohol andpropargyl alcohol. In a particular embodiment, the isopropyl alcohol andpropargyl alcohol are present at approximately isopropyl alcohol, 0.067wt %, and propargyl alcohol, 0.022 wt %.

The ethoxylate can comprise ethoxylated nonylphenol, which can bepresent at approximately 0.022 wt %.

The ketone can comprise methyl vinyl ketone, which can present atapproximately 0.022 wt %.

In a particular embodiment, the composition can comprise: HCl, 55 wt %;urea, 42 wt %; complex substituted keto-amine-hydrochloride, 0.067 wt %;isopropyl alcohol, 0.067 wt %; ethoxylated nonylphenol, 0.022 wt %;propargyl alcohol, 0.022 wt %; methyl vinyl ketone, 0.022 wt %; acetone,0.022 wt %; and acetophenone, 0.0022 wt %.

The composition can be used as a base for a plurality of dilution levelsto be used for different applications. For example, sufficient water canbe added to the composition to dilute the base in a range of 1:1 to 6:1water:base.

A plurality of exemplary compositions using the composition describedabove can be used as a base for removing cementitious material from avariety of surfaces. For example, concrete can be removed from equipmentwith a composition comprising: base (25 wt %), nonylphenol 9.5 mole(0.25 wt %), quaternary ammonium compounds (0.15 wt %), glycol ether EB(0.20 wt %), and water (74.4 wt %). This formula can be used on, forexample, ready-mixed concrete, cement, and masonry, although these usesare not intended to be limiting.

Another composition for use as concrete removing agent on equipment cancomprise: base (35 wt %), nonylphenol 9.5 mole (0.25 wt %), quaternaryammonium compounds (0.15 wt %), glycol ether EB (0.20 wt %), and water(64.4 wt %). This formula can be used on, for example, ready-mixedconcrete, cement, and masonry, although these uses are not intended tobe limiting.

Yet another composition can be used as an efflorescence remover oncementitious materials (concrete block, brick, precast, paver, cement,and masonry). An exemplary formula for this composition is: base (15 wt%), nonylphenol 9.5 mole (0.25 wt %), quaternary ammonium compounds(0.15 wt %), glycol ether EB (0.20 wt %), and water (84.4 wt %). Thisformula can be used on, for example, concrete block, brick, precast,cement, and masonry, although these uses are not intended to belimiting.

A basic composition for use as a concrete removing agent on tools andequipment includes base (25 wt %) and water (75 wt %). This formula canbe used on, for example, ready-mixed concrete, cement, and masonry,although these uses are not intended to be limiting.

Another composition for use as a concrete removing agent on equipmentcomprises base (60.0 wt %), nonylphenol 9.5 mole (0.25 wt %), quaternaryammonium compounds (0.15 wt %), glycol ether EB (0.20 wt %), and water(39.4 wt %). This formula can be used on, for example, ready-mixedconcrete, cement, and masonry, although these uses are not intended tobe limiting.

DEFINITIONS

The term “alcohol”, as used herein, unless otherwise indicated, includesa compound in which the hydroxyl functional group (—OH) is bound to acarbon atom. In particular, this carbon center should be saturated,having single bonds to three other atoms. For example, ethanol,isopropanol, propanol, butanol, propargyl alcohol, nonylphenol and thelike.

The term “ethoxylated” as used herein refers to the incorporation of anethoxy moiety to a given substrate structure, wherein ethoxy refers tothe structure CH3CH2O—, wherein the ethoxy group is bound through theoxygen atom. For example, ethoxylated nonylphenol. The term “ethoxylate”refers to the anionic form of ethoxy or an ethoxylated compound in saltform.

The term “ketone” as used herein refers to a radical having thestructure —C(O)—R1 (such as acetyl, —C(O)CH3) or —R1-C(O)—R2-. Theketone can be attached to another group through R1 or R2. R1 or R2 canbe alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl or aryl, forexample methyl vinyl ketone or acetophenone, or R1 or R2 can be joinedto form a 3- to 12-membered ring.

The term “keto-amine” as used herein refers to chemical moietiescontaining the structure —C(═O)—N(R1)R2 wherein R1 and R2 areindependently H, a bond, lower alkyl, cycloalkyl, phenyl orheterocycloalkyl. The keto-aminee can be attached to another groupthrough R1 or R2. R1 or R2 can be alkyl, alkenyl, alkynyl, cycloalkyl,heterocyclyl or aryl, or R1 or R2 can be joined to form a 3- to12-membered ring.

The term “keto-amine hydrochloride” as used herein refers to thehydrochloride salt of the keto-amine as above described.

The application provides a method for solubilizing calcium carbonate inan aqueous suspension or dispersion of calcium carbonate, the methodcomprising:

providing a composition comprising HCl, urea, complex substitutedketo-amine-hydrochloride, an alcohol, an ethoxylate, and a ketone;

adding the composition to an aqueous suspension or dispersion of calciumcarbonate; and

permitting the composition to solubilize the aqueous suspension ordispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application alternatively provides the above method, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application alternatively provides the above method, furthercomprising diluting the composition by 20-90% by volume composition inwater prior to the composition adding step.

The application alternatively provides the above method, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application alternatively provides any one of the above methods,wherein the composition is used for pickling treatments.

The application alternatively provides any one of the above methods,wherein the composition is used for electronic submersible pumptreatments (ESPs).

The application alternatively provides any one of the above methods,wherein the composition is used for hydraulic fracturing.

The application alternatively provides any one of the above methods,wherein the composition is used for perforation cleaning and debrisremoval.

The application alternatively provides any one of the above methods,wherein the composition is used for toe preparation treatments thatreplace the use of acetic acid blends.

The application alternatively provides any one of the above methods,wherein the composition is used for cement squeeze treatments.

The application alternatively provides any one of the above methods,wherein the composition is used for injection well treatments.

The application alternatively provides any one of the above methods,wherein the composition is used for disposal well treatments.

The application alternatively provides any one of the above methods,wherein the method is used for pH adjustment of recycled frac waterand/or flow-back fluids.

The application alternatively provides any one of the above methods,wherein the method is used for pH adjustment fluid to assist with thehydration of gelled based systems.

The application alternatively provides any one of the above methods,wherein the composition is used for breaking gelled fracturing systemsto replace the use of dangerous oxidizing agents.

The application alternatively provides any one of the above methods,wherein the composition is used for a treatment fluid to unstick adrilling rig.

The application alternatively provides any one of the above methods,wherein the composition is used for acid fracture.

The application alternatively provides any one of the above methods,wherein the composition is used for spearhead acid squeeze soaks.

The application alternatively provides any one of the above methods,wherein the composition is used for filter cake removal.

The application provides a method for pickling treatments comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for electronic submersible pumptreatments (ESPs) comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for hydraulic fracturing comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for perforation cleaning and debrisremoval comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for toe preparation treatments thatreplace the use of acetic acid blends comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for cement squeeze treatmentscomprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for injection well treatmentscomprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for disposal well treatmentscomprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for pH adjustment of recycled fracwater and/or flow-back fluids comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for pH adjustment fluid to assist withthe hydration of gelled based systems comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for breaking gelled fracturing systemsto replace the use of dangerous oxidizing agents comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method using a fluid to unstick a drillingrig comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for acid fracture comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for spearhead acid squeeze soakingcomprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

The application provides a method for filter cake removal comprising:

solubilizing calcium carbonate in an aqueous suspension or dispersion ofcalcium carbonate, the method including the steps of

-   -   i) providing a composition comprising HCl, urea, complex        substituted keto-amine-hydrochloride, an alcohol, an ethoxylate,        and a ketone;    -   ii) adding the composition to an aqueous suspension or        dispersion of calcium carbonate; and    -   iii) permitting the composition to solubilize the aqueous        suspension or dispersion of calcium carbonate.

The application provides the above method, wherein the alcohol comprisesat least one of isopropyl alcohol and propargyl alcohol.

The application provides any of the above methods, wherein theethoxylate comprises ethoxylated nonylphenol and the ketone comprisesmethyl vinyl ketone.

The application provides any of the above methods, further comprisingdiluting the composition by 20-90% by volume composition in water priorto the composition adding step.

The application provides any of the above methods, wherein thecomposition comprises: HCl, 55 wt %; urea, 42 wt %; complex substitutedketo-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %;ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %;methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone,0.0022 wt %.

A method for performing hydraulic fracturing of an oil or a gas wellcomprises providing a composition such as that described above andinserting the composition into an oil well or a gas well to assist inperforming hydraulic fracturing thereof.

A method for adjusting a pH of a drilling fluid comprises providing acomposition such as described above and adding the composition to adrilling fluid for a well to assist in adjusting a pH thereof. Thecomposition can be diluted to 20-90% by volume composition in water.

A method for adjusting and maintaining a pH of a process fluid comprisesproviding a composition such as described above and adding thecomposition to a process fluid to adjust and maintain a pH thereof. Theprocess fluid can comprise at least one of a processing fluid fortextiles, a processing fluid for paper manufacturing, industrial processwater, waste water, industrial discharge water, and industrial recyclingwater. The composition can be diluted by 10-85% by volume composition inwater, for example.

A method for solubilizing calcium carbonate in an aqueous suspension ordispersion of calcium carbonate comprises providing a composition suchas described above and adding the composition to an aqueous suspensionor dispersion of calcium carbonate. The composition is permitted tosolubilize the aqueous suspension or dispersion of calcium carbonate.The composition can be diluted by 10-95% by volume composition in water,for example.

A method for removing a foulant from a fluid-handling element comprisesproviding a composition comprising HCl, urea, complex substitutedketo-amine-hydrochloride, an alcohol, an ethoxylate, and a ketone;adding the composition to a fouled fluid-handling element; andpermitting the composition to solubilize the foulant.

In one sub-embodiment, the fluid-handling element can comprise a wasteplumbing system and the foulant can comprise a salt of at least one ofcalcium and magnesium. In this embodiment the composition can be dilutedprior to the adding step to 10-65% by volume composition in water.

In another sub-embodiment, the fluid-handling element can comprise anindustrial boiler system and the foulant can comprise a salt of at leastone of calcium and magnesium. In this embodiment the composition can bediluted prior to the adding step by 5-70% by volume composition inwater.

In a further sub-embodiment, the fluid-handling element can comprise aplumbing element of a marine vessel and the foulant can comprise atleast one of a salt of at least one of calcium and magnesium, a marineorganism such as arthropods such as cirripedia or crustaceans, andsludge. In this embodiment the composition can be diluted prior to theadding step by 5-80% by volume composition in water. Here the plumbingelement can comprises a waste plumbing element, and the diluting cancomprise diluting the composition by 10-65% by volume composition inwater. The plumbing element can also comprise an internal plumbingelement, and the diluting can comprise diluting the composition by 5-50%by volume composition in water. Alternatively, the plumbing element cancomprise an element in a propulsion system, such as, but not intended tobe limited to, inboard, outboard, inboard/outboard, surface drive, orjet drive propulsion engine systems, and the diluting can comprisediluting the composition by 5-80% by volume composition in water.

A method for removing a foulant from a surface of a marine vesselcomprises providing a composition comprising HCl, urea, complexsubstituted keto-amine-hydrochloride, an alcohol, an ethoxylate, and aketone; applying the composition to a fouled surface of a marine vessel;and permitting the composition to solubilize the foulant. The surfacecan comprise, for example, a marine hull. If desired, the compositioncan be diluted by 5-95% by volume composition in water. The foulant cancomprise at least one of a salt of at least one of calcium andmagnesium, a marine organism such as arthropods such as cirripedia orcrustaceans, and sludge.

A method for lowering a salt and bicarbonate level in an irrigationsystem comprises providing a composition comprising HCl, urea, complexsubstituted keto-amine-hydrochloride, an alcohol, an ethoxylate, and aketone; diluting the composition to 5-60% by volume composition inwater; adding the composition to a fouled fluid-transporting element ofan irrigation system; and permitting the composition to solubilize thefoulant.

A method for acidizing turf and for lowering a salt and bicarbonatelevel in at least one of turf and turf growing medium comprisesproviding a composition comprising HCl, urea, complex substitutedketo-amine-hydrochloride, an alcohol, an ethoxylate, and a ketone; andadding the composition to at least one of turf and turf growing medium.The composition can be diluted to 1-35% by volume composition in water.

A method for acid fracturing in a cased or open hole via single ormultistage wherein the formation of fracture pressure is a keytechnological improvement for stimulation in many types of vertical orhorizontal well formations, wherein this technology can be used in placeof typical mineral or organic acids as are typically used in suchapplications.

A method for filter cake removal wherein the reservoir production isactivated without damaging the formation after drilling. Wherein, thistechnology can be used to remove the filter cake produced during thedrilling procedure.

A method of pumping a volume of acid prior to a volume of fluid tofacilitate the cleaning of perforations and assist in the lowering ofpressures required to break a formation.

A method stimulate a well to improve flow or to remove damage wherebyacid is injected into the well, penetrating the rock pores at pressuresbelow fracture pressure, wherein the acids dissolve the sediments andmud solids in the pores of the rocks preventing permeability of therock.

A method that to restore permeability by removing damage around awellbore with acid or matrix acid thereby improving sandstone andcarbonate well productivity.

A method for removal of scale or other deposits from perforation and theperforations associated with well completion,

A method of using acid to treat scaling issues, usually calcium based,in wells that are used to produce water with the oil or gas or wells inwhich water is injected back into the ground.

A method of using acid to lower the pH of any fluid system in theproduction of oil or gas.

One of skill in the art will recognize that these compositions andmethods of use are not intended to be limiting, and variations iningredients, proportions, and methods of use can be made withoutdeparting from the spirit of the invention.

Having now described the invention and use of preferred embodimentsthereof, and the advantageous new and useful results obtained thereby,the new and useful constructions, and reasonable equivalents thereofobvious to those skilled in the art, are set forth in the appendedclaims.

What is claimed is:
 1. A method for performing hydraulic fracturing of at least one of an oil well and a gas well, the method comprising: providing a composition comprising HCl, urea, complex substituted keto-amine-hydrochloride, at least one alcohol selected from the group consisting of isopropyl alcohol and propargyl alcohol, an ethoxylate, and at least one ketone selected from the group consisting of methyl vinyl ketone, acetone, and acetophenone; and inserting the composition into at least one of an oil well and a gas well to assist in performing hydraulic fracturing thereof.
 2. The method of claim 1, wherein the ethoxylate comprises an ethoxylated nonylphenol.
 3. The method of claim 1, further comprising diluting the composition by 20-90% by volume composition in water.
 4. A method for adjusting a pH of a drilling fluid, the method comprising: providing a composition comprising HCl, urea, complex substituted keto-amine-hydrochloride, at least one alcohol selected from the group consisting of isopropyl alcohol and propargyl alcohol, an ethoxylate, and at least one ketone selected from the group consisting of methyl vinyl ketone, acetone, and acetophenone; and adding the composition to a drilling fluid to assist in adjusting a pH thereof.
 5. The method of claim 4, wherein the ethoxylate comprises an ethoxylated nonylphenol.
 6. The method of claim 4, further comprising diluting the composition by 20-90% by volume composition in water.
 7. The method of claim 5, wherein the composition comprises: HCl, 55 wt %; urea, 42 wt %; complex substituted keto-amine-hydrochloride, 0.067 wt %; isopropyl alcohol, 0.067 wt %; ethoxylated nonylphenol, 0.022 wt %; propargyl alcohol, 0.022 wt %; methyl vinyl ketone, 0.022 wt %; acetone, 0.022 wt %; and acetophenone, 0.0022 wt %. 